Curable polycyclic compounds and process for the production thereof

ABSTRACT

The present invention discloses a curable polycyclic compound represented by the following formula (1):  
                 
 
{wherein A is a di- to hexa-valent group derived from a polycyclic hydrocarbon compound; R 1  is an alkyl group of 1 to 4 carbon atoms, a perfluoroalkyl group of 1 to 4 carbon atoms, or a fluorine atom; n is an integer of 0 to 2; m is an integer of 2 to 4; and Y is a group represented by the following formula (2) or (3):  
                 
 
(wherein R 2 , R 3 , R 5  and R 6  are each independently a hydrogen atom, a fluorine atom or an alkyl group of 1 to 4 carbon atoms; R 4  is a methyl group or an ethyl group; and p and q are each independently an integer of 0 to 4)}.

TECHNICAL FIELD

The present invention relates to novel curable polycyclic compoundsuseful as a raw material for encapsulant, adhesive, etc.; a process forproduction thereof; a curable composition prepared using the compound;an encapsulant for light-emitting diode, comprising the curablecomposition; and a light-emitting diode encapsulated with theencapsulant. The curable polycyclic compounds have oxetanyl group orepoxy group as a functional group capable of giving rise to a curingreaction.

BACKGROUND ART

Polycyclic hydrocarbon compounds show non-aromaticity, have a stiffmolecule, have a unique structure and accordingly are drawing attentionin various fields. There are known, for example, diallyladamantanedicarboxylate (JP 1985-100537 A) andadamantanedi(meth)acrylate derivatives (JP 1988-307844 A), each as amonomer for plastic lens superior in optical properties and heatresistance.

There are also known particular adamantane compounds having (meth)acrylgroup (JP 2000-327950 A and JP 2000-327994 A), as a monomer for coatingcomposition superior in adhesivity, light resistance, chemicalresistance and hardness or as a monomer for coating.

Meanwhile, in recent years, there has been a remarkable progress withrespect to the light-emitting diode (hereinafter, abbreviated as LED)which is a semiconductor light-emitting device produced with a compoundsemiconductor. As the light-emitting material therefor, there weredeveloped aluminum•indium•gallium•phosphorus (AlInGaP) for red to bitterorange color light and gallium nitride (GaN) for blue color light. Therewas also realized a near-ultraviolet LED of 400 nm or shorter (e.g. 365nm or 370 nm).

There was also achieved a white LED by, for example, combining afluorescent material with a blue LED or a near-ultraviolet LED.

LED has various advantages such as long life, high thermal stability,easy light control, low operating voltage and the like. Owing to thehigh evaluation of LED particularly for the high light-emittingefficiency and high reliability, active application of LED is beingpushed forward in the fields such as display, display panel, vehiclelighting, signal lamp, mobile telephone, video camera and the like. Asthe package shape of LED, there have been developed various packageshapes suited for applications, such as bullet-shaped lamp, surfacemounting type and the like. With respect to, in particular, white LED,its application to lighting is being pushed forward and there is highexpectation as an alternate light source for conventional incandescentlamp, halogen lamp, fluorescent lamp, etc. However, for the wide spreadthereof, higher luminance and improved light source efficiency areneeded.

Ordinarily, LED is encapsulated with a transparent encapsulantcomprising an epoxy resin, a silicone resin or the like, in order toprotect the semiconductor device accommodated inside. Of the materialsfor encapsulant, the epoxy resin, in particular, has high adhesivity andhigh handleablity, is inexpensive, and is a material suitable forpractical use; therefore, it is in wide use for encapsulation of LED.Meanwhile, the encapsulant for LED is required to have high lightresistance in association with the above-mentioned move of LED toshorter wavelength. Further, in association with the move of LED tohigher luminance, the encapsulant for LED is strongly required to havehigh heat resistance capable of withstanding the heat generated by theLED element.

Conventional epoxy resins such as bisphenol A type glycidyl ether andthe like, used as a component of encapsulant tend to be deterioratedowing to the move to shorter wavelength or the heat generation of LEDdevice. Consequently, there is a problem that the resin gives rise toyellowing, inviting a reduction in LED luminance and a change in LEDcolor tone.

Various investigations have been made in order to achieve the abovetasks. For example, light resistance of resin was slightly increased byadding an alicyclic epoxy to a hydrogenated bisphenol A type glycidylether (JP 2003-73452 A). However, the resulting resin has no sufficientweather resistance practically and further has lower heat resistance,causing discoloration. Also, it was attempted to further add, to theresin, a phosphorus-based antioxidant. In this case, an effect ofsuppressing the discoloration caused by heat was seen but there was areduction in light resistance.

With respect to polycyclic epoxy compounds, there is a case in which anepoxy compound having only one epoxy group, such as 1-adamantylglycidylether was produced; however, there is no case in which an epoxy compoundhaving two or more epoxy groups was produced at a high yield at a highpurity.

As the conventional process for producing 1-adamantylglycidyl ether,there is known a process which comprises reacting 1-adamantanol withepichlorohydrin in the presence of a catalytic amount of tintetra-chloride and then allowing sodium hydroxide to act on the reactionproduct to obtain 1-adamantylglycidyl ether (The Journal of OrganicChemistry USSR, Vol. 27, No. 6, pp. 1089-1092, 1991).

The process gives a yield of 61% which is not bad. In this process,however, tin tetra-chloride (which is a Lewis acid) is used as thecatalyst. For the safety reason of the catalyst, the solvent usable islimited to low-polarity solvents such as halides. Hence, in productionof 1-adamantylglycidyl ether, when the starting raw material is changedfrom 1-adamantanol to an adamantanepolyol having two or more hydroxylgroups (which has very low solubility in low-polar solvents), thereactivity thereof is not certain. Further, there is a fear thatepichlorohydrin itself polymerizes in the presence of an acid such asLewis acid and the polymerizate remains as an impurity. As a process forobtaining a glycidyl ether from an alcohol, there is generallyconsidered a process which comprises reacting an alcohol with an alkalimetal or the like to synthesize an alcoholate and contacting thealcoholate with epichlorohydrin or epibromohydrin. However, there is nocase in which this process has been applied to any polycyclic hydroxycompound having two or more hydroxyl groups.

DISCLOSURE OF THE INVENTION

Each of the cured material obtained by curing a polycyclic hydrocarboncompound contains a polycyclic hydrocarbon skeleton in the molecule hassuperior optical properties and heat resistance. In the applicationsfields of such cured materials where the above properties are required,however, there are also required other properties which are differentdepending upon individual applications. In order to satisfy suchdiversified requirements, it is essential to develop a novel curablecompound containing a polycyclic hydrocarbon skeleton.

In other words, the method of curing a curable compound containing apolycyclic hydrocarbon skeleton, to obtain a resin, is promising as auseful means for obtaining a resin superior in optical properties andheat resistance; however, such curable compounds currently known arelimited and accordingly their applications are limited as well at thepresent stage.

In order to diversify the technique being employable, the presentinvention aims at providing a novel curable compound containing apolycyclic hydrocarbon skeleton in the molecule, which is usefulindustrially.

The present inventors made a study in order to achieve the above aim. Asa result, it was found that novel curable polycyclic hydrocarboncompounds obtained by introducing, into a polycyclic hydrocarboncompound, oxetanyl group and/or epoxy group as polymerizable functionalgroup can achieve the above aim.

These compounds, when cured, give a cured material high in opticalproperties and light resistance. It was further found that thesecompounds give a small shrinkage when cured and, therefore, can besuitably used as an adhesive or an encapsulant for semiconductor laser,both requiring optical properties, high heat resistance, etc.

The present invention has been completed based on these findings.

The present invention is as described below.[1] A curable polycyclic compound represented by the following formula(1):

{wherein A is a di- to hexa-valent group derived from a polycyclichydrocarbon compound; R¹ is an alkyl group of 1 to 4 carbon atoms, aperfluoroalkyl group of 1 to 4 carbon atoms, or a fluorine atom; n is aninteger of 0 to 2; m is an integer of 2 to 4; and Y is a grouprepresented by the following formula (2):

(wherein R² and R³ are each independently a hydrogen atom, a fluorineatom or an alkyl group of 1 to 4 carbon atoms; R⁴ is a methyl group oran ethyl group; and p is an integer of 0 to 4), or a group representedby the following formula (3):

(wherein R⁵ and R⁶ are each independently a hydrogen atom, a fluorineatom or an alkyl group of 1 to 4 carbon atoms; and q is an integer of 0to 4)}.[2] A curable polycyclic compound according to [1], wherein the formula(1) is the following formula (4):

{wherein R¹ is an alkyl group of 1 to 4 carbon atoms, a perfluoroalkylgroup of 1 to 4 carbon atoms, or a fluorine atom; a is an integer of 0to 2; b is an integer of 0 to 2; and Y is a group represented by thefollowing formula (2):

(wherein R² and R³ are each independently a hydrogen atom, a fluorineatom or an alkyl group of 1 to 4 carbon atoms; R⁴ is a methyl group oran ethyl group; and p is an integer of 0 to 4), or a group representedby the following formula (3):

(wherein R⁵ and R⁶ are each independently a hydrogen atom, a fluorineatom or an alkyl group of 1 to 4 carbon atoms; and q is an integer of 0to 4)}.[3] A curable polycyclic compound according to [2], wherein, in theformula (4), a, p and q are 0 (zero).[4] A curable polycyclic compound according to [1], wherein the contentof the halogen molecule or halogen ion contained as an impurity is 100to 2,000 ppm.[5] A curable polycyclic compound represented by the general formula (6)or (7):

{wherein A, R¹, R², R³, n and p have the same definitions as in theformula (1); and s is an integer of 1 to 3}

{wherein A, R¹, R⁵, R⁶, n and q have the same definitions as in theformula (1); and s′ is an integer of 1 to 3}.[6] A curable composition characterized by comprising a curablepolycyclic compound set forth in any of [1] to [3] and a curing agent.[7] A curable composition according to [6], wherein the curablepolycyclic compound is a compound represented by the following formula(4):

{wherein R¹ is an alkyl group of 1 to 4 carbon atoms, a perfluoroalkylgroup of 1 to 4 carbon atoms, or a fluorine atom; a is an integer of 0to 2; b is an integer of 0 to 2; and Y is a group represented by thefollowing formula (3):

(wherein R⁵ and R⁶ are each independently a hydrogen atom, a fluorineatom or an alkyl group of 1 to 4 carbon atoms; and q is an integer of 0to 4)}.[8] An encapsulant for light-emitting diode, comprising a curablecomposition set forth in [6] or [7].[9] A light-emitting diode encapsulated by an encapsulant set forth in[8].[10] A process for producing a polycyclic epoxy compound represented bythe following formula (8):

{wherein A is a di- to hexa-valent group derived form a polycyclichydrocarbon compound; R¹ is an alkyl group of 1 to 4 carbon atoms, aperfluoroalkyl group of 1 to 4 carbon atoms, or a fluorine atom; n is aninteger of 0 to 2; m is an integer of 2 to 4; and Z is a grouprepresented by the above formula (3):

(wherein R⁵ and R⁶ are each independently a hydrogen atom, a fluorineatom or an alkyl group of 1 to 4 carbon atoms; and q is an integer of 0to 4)}, which process is characterized by comprising the following steps(a) to (c):

a step (a) of reacting a polycyclic hydroxy compound represented by thefollowing formula (9):

{wherein A, R¹, n and m have the same definitions as in the formula (8);R⁷ and R⁸ are each independently a hydrogen atom, a fluorine atom or analkyl group of 1 to 4 carbon atoms; and r is an integer of 0 to 4}, withan alkali metal, an alkaline earth metal or an organometal compoundcontaining such a metal to obtain an alcoholate,

a step (b) of reacting the alcoholate obtained in the step (a), with anallyl group-containing compound represented by the following formula(10):X—CH₂—CH═CH₂  (10)(wherein X is a halogen atom or a sulfonyloxy group) to obtain apolycyclic allyl compound represented by the following formula (11):

[wherein A, R¹, n and m have the same definitions as in the formula (8);and W is a group represented by the following formula (12):

{wherein R⁵, R⁶ and q have the same definitions as in the formula (3)}],and

a step (c) of oxidizing the polycyclic allyl compound obtained in thestep (b).[11] A polycyclic allyl compound represented by the following formula(11):

{wherein A is a di- to hexa-valent group derived from a polycyclichydrocarbon compound; R¹ is an alkyl group of 1 to 4 carbon atoms, aperfluoroalkyl group of 1 to 4 carbon atoms, or a fluorine atom; n is aninteger of 0 to 2; m is an integer of 2 to 4; and W is a grouprepresented by the following formula (12):

(wherein R⁵ and R⁶ are each independently a hydrogen atom, a fluorineatom or an alkyl group of 1 to 4 carbon atoms; and q is an integer of 0to 4)}.

In each of the compounds represented by the above general formulas, wheneach group of R¹ to R⁸, A, Y, X, Z and W is bonded in plurality in themolecule, they may be the same group or different groups.

As a raw material for adhesive or encapsulant, there have been usedaliphatic curable compounds containing oxetanyl group or epoxy group,such as hydrogenated bisphenol A type and the like, and aromatic curablecompounds containing oxetanyl group or epoxy group, such as bisphenol Atype, novolac type and the like. Cured materials obtained from theformer compounds have a problem of low heat resistance. Cured materialsobtained from the latter compounds have a problem of low lightresistance. The cured materials obtained from the latter compounds arelow in transparency particularly in a short-wavelength region and,accordingly, when irradiated with an ultraviolet light, cause colordevelopment with the lapse of time and show a reduction in mechanicalproperties. Further, the cured materials obtained from the lattercompounds have a problem of low refractive index.

In contrast, the cured materials obtained from the curable polycycliccompounds of the present invention are less in these problems.

The curable polycyclic compounds of the present invention arecharacterized by giving a cured material superior in optical properties,heat resistance and light resistance and being small shrinkage whencured. Therefore, the compounds can be suitably used as a raw materialfor various plastic substrates, a raw material for coating, a rawmaterial for adhesive, a raw material for encapsulant, etc.

The cured material of the curable composition of the present inventionis superior in light resistance, heat resistance, etc. and has highadhesivity to light-emitting diode. Therefore, the curable compositionof the present invention is suitable as an encapsulant forshort-wavelength LED (e.g. near-ultraviolet LED or white LED), etc.

BEST MODE FOR CARRYING OUT THE INVENTION

The curable polycyclic compounds of the present invention arerepresented by the above-shown formula (1), wherein oxetanyl groupand/or epoxy group each represented by group —Y is bonded to carbonatoms of a polycyclic hydrocarbon skeleton. Since the group —Y has achemical structure containing an ether bond, the compounds can beproduced easily by an ordinary chemical reaction.

In the formula (1), A is a di- to hexa-valent group derived from apolycyclic hydrocarbon compound. As the group A, there can be mentioneddi- to hexa-valent groups derived from adamantane, norbornane,bicyclooctane, bicyclononane, tetrahydrodicyclopentadiene,1-ethyladamantane, 1-ethylnorbornane, 1-ethylbicyclooctane,1-ethylbicyclononane, 1-ethyltetrahydrodicyclopentadiene,5,7-dimethyladamantane, 1,4-dimethylnorbornane,1,5-dimethylbicyclooctane, 1,5-dimethylbicyclononane,1,5-dimethyltetrahydrodicyclopentadiene, 1-fluoroadamantane,1-fluoronorbornane, 1-fluorobicyclooctane, 1-fluorobicyclononane,1-fluorotetrahydrodicyclopentadiene, 1-trifluoromethyladamantane,1-trifluoromethylnorbornane, 1-trifluoromethylbicyclooctane,1-trifluoromethylbicyclononane,1-trifluoromethyltetrahydrodicyclopentadiene, 1,3-difluoroadamantane,1,4-difluoronorbornane, 1,5-difluorobicyclooctane,1,5-difluorobicyclononane, 1,5-difluorotetrahydrodicyclopentadiene, etc.

Particularly preferred are di- to hexa-valent groups derived fromadamantane having a stiff skeleton. Here, the di- to hexa-valent groupderived from a polycyclic hydrocarbon compound means a group which hasbeen formed by elimination of 2 to 6 hydrogen atoms from the polycyclichydrocarbon skeleton of a polycyclic hydrocarbon compound and whereinthe hydrogen-eliminated sites of the polycyclic hydrocarbon skeletonhave become bonds (free valences). There is no particular restriction asto the sites of the bonds on the skeleton.

In the formula (1), R¹ means an alkyl group of 1 to 4 carbon atoms, aperfluoroalkyl group of 1 to 4 carbon atoms, or a fluorine atom. As thealkyl group, there can be mentioned methyl group, ethyl group, propylgroup, isopropyl group, butyl group, etc. As the perfluoroalkyl group,there can be mentioned perfluoromethyl group, perfluoroethyl group,perfluorobutyl group, etc. Of these groups, methyl group is preferred asR¹ for the easy synthesis of the compound of the formula (1). n, whichindicates the number of R¹ present in the molecule of the compound ofthe formula (1), is an integer of 0 to 2. n is preferably 2 for the easysynthesis of the compound of the formula (1) and the high heatresistance of a cured material obtained by curing of the compound of theformula (1).

When n is 2, two R¹s may be the same or different from each other. Thetwo R¹s are preferably the same for the easy synthesis of the compoundof the formula (1).

When n is 1 or 2, there is no particular restriction as to the site(s)to which R¹(s) bonds (bond), as long as the site(s) is (are) differentfrom the sites to which oxetanyl group or epoxy group bonds.

In the formula (1), Y indicates a group represented by the formula (2)or (3). Incidentally, R² and R³ of the formula (2) or R⁵ and R⁶ of theformula (3) are each independently a hydrogen atom, a fluorine atom oran alkyl group of 1 to 4 carbon atoms. The alkyl group of 1 to 4 carbonatoms has the same meaning as substituting group of 1 to 4 carbon atoms,of R¹. R⁴ is a methyl group or an ethyl group.

p and q are each an integer of 0 to 4. p and q are preferably an integerof 0 or 1, more preferably an integer of 0, for the easy synthesis ofthe compound of the formula (1) and the good heat resistance of thecompound. m, which indicates the number of the bonding group —Y whichbonds to A, is an integer of 2 to 4. m is preferably 2 or 3, morepreferably 2 for the high heat resistance and high flexibility of thecured material obtained. As to the bonding sites of the group —Y, it ispreferred that at least two groups —Y bond to bridge head carbons; whenm is 3 or 4, there is no particular restriction as to the bondingsite(s) of remaining group(s) —Y.

In the formula (2), R⁴ is a methyl group or an ethyl group.

As preferred specific examples of the curable polycyclic compoundrepresented by the formula (1), there can be mentioned polycyclichydrocarbon compounds having oxetanyl group, such as1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane,2,5-bis[(3-ethyloxetan-3-yl)methoxy]norbornane,2,6-bis[(3-ethyloxetan-3-yl)methoxy]bicyclooctane,2,7-bis[(3-ethyloxetan-3-yl)methoxy]bicyclononane,2,7-bis[(3-ethyloxetan-3-yl)methoxy]tetrahydrodicyclopentadiene,5,7-dimethyl-1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane,1,4-dimethyl-2,5-bis[(3-ethyloxetan-3-yl)methoxy]norbornane,1,5-dimethyl-2,6-bis[(3-ethyloxetan-3-yl)methoxy]bicyclooctane,1,5-dimethyl-2,7-bis[(3-ethyloxetan-3-yl)methoxy]bicyclononane,1,5-dimethyl-2,7-bis[(3-ethyloxetan-3-yl)methoxy]tetrahydrodicyclopentadiene,1,3,5-tris[(3-ethyloxetan-3-yl)methoxy]adamantane,2,3,5-tris[(3-ethyloxetan-3-yl)methoxy]norbornane,2,4,6-tris[(3-ethyloxetan-3-yl)methoxy]bicyclooctane,2,4,7-tris[(3-ethyloxetan-3-yl)methoxy]bicyclononane,2,5,7-tris[(3-ethyloxetan-3-yl)methoxy]tetrahydrodicyclopentadiene,1,3-bis[(3-ethyloxetan-3-yl)methoxymethyl]adamantane,2,5-bis[(3-ethyloxetan-3-yl)methoxymethyl]norbornane,2,6-bis[(3-ethyloxetan-3-yl)methoxymethyl]bicyclooctane,2,7-bis[(3-ethyloxetan-3-yl)methoxymethyl]bicyclononane,2,7-bis[(3-ethyloxetan-3-yl)methoxymethyl]tetrahydrodicyclopentadiene,1,3,5-tris[(3-ethyloxetan-3-yl)methoxymethyl]adamantane,2,3,5-tris[(3-ethyloxetan-3-yl)methoxymethyl]norbornane,2,4,6-tris[(3-ethyloxetan-3-yl)methoxymethyl]bicyclooctane,2,4,7-tris[(3-ethyloxetan-3-yl)methoxymethyl]bicyclononane,2,5,7-tris[(3-ethyloxetan-3-yl)methoxymethyl]tetrahydrodicyclopentadieneand the like.

There can also be mentioned polycyclic hydrocarbon compounds havingepoxy group, such as 1,3-bis(glycidyloxy)adamantane,2,5-bis(glycidyloxy)norbornane, 2,6-bis(glycidyloxy)bicyclooctane,2,7-bis(glycidyloxy)bicyclononane,2,7-bis(glycidyloxy)tetrahydrodicyclopentadiene,5,7-dimethyl-1,3-bis(glycidyloxy)adamantane,1,4-dimethyl-2,5-bis(glycidyloxy)norbornane,1,5-dimethyl-2,6-bis(glycidyloxy)bicyclooctane,1,5-dimethyl-2,7-bis(glycidyloxy)bicyclononane,1,5-dimethyl-2,7-bis(glycidyloxy)tetrahydrodicyclopentadiene,1,3,5-tris(glycidyloxy)adamantane, 2,3,5-tris(glycidyloxy)norbornane,2,4,6-tris(glycidyloxy)bicyclooctane,2,4,7-tris(glycidyloxy)bicyclononane,2,5,7-tris(glycidyloxy)tetrahydrodicyclopentadiene,1,3-bis(glycidyloxymethyl)adamantane,2,5-bis(glycidyloxymethyl)norbornane,2,6-bis(glycidyloxymethyl)bicyclooctane,2,7-bis(glycidyloxymethyl)bicyclononane,2,7-bis(glycidyloxymethyl)tetrahydrodicyclopentadiene,1,3,5-tris(glycidyloxymethyl)adamantane,2,3,5-tris(glycidyloxymethyl)norbornane,2,4,6-tris(glycidyloxymethyl)bicyclooctane,2,4,7-tris(glycidyloxymethyl)bicyclononane,2,5,7-tris(glycidyloxymethyl)tetrahydrodicyclopentadiene and the like.

Of these compounds, particularly preferred for the easy production andthe capability of giving a cured material of high heat resistance arepolycyclic hydrocarbon compounds having oxetanyl group, such as1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane,2,5-bis[(3-ethyloxetan-3-yl)methoxy]norbornane,2,6-bis[(3-ethyloxetan-3-yl)methoxy]bicyclooctane,2,7-bis[(3-ethyloxetan-3-yl)methoxy]bicyclononane,2,7-bis[(3-ethyloxetan-3-yl)methoxy]tetrahydrodicyclopentadiene,1,3,5-tris[(3-ethyloxetan-3-yl)methoxy]adamantane,2,3,5-tris[(3-ethyloxetan-3-yl)methoxy]norbornane,2,4,6-tris[(3-ethyloxetan-3-yl)methoxy]bicyclooctane,2,4,7-tris[(3-ethyloxetan-3-yl)methoxy]bicyclononane,2,5,7-tris[(3-ethyloxetan-3-yl)methoxy]tetrahydrodicyclopentadiene andthe like; and polycyclic hydrocarbon compounds having epoxy group, suchas 1,3-bis(glycidyloxy)adamantane, 2,5-bis(glycidyloxy)norbornane,2,6-bis(glycidyloxy)bicyclooctane, 2,7-bis(glycidyloxy)bicyclononane,2,7-bis(glycidyloxy)tetrahydrodicyclopentadiene,1,3,5-tris(glycidyloxy)adamantane, 2,3,5-tris(glycidyloxy)norbornane,2,4,6-tris(glycidyloxy)bicyclooctane,2,4,7-tris(glycidyloxy)bicyclononane,2,5,7-tris(glycidyloxy)tetrahydrodicyclopentadiene and the like.

Of the present curable polycyclic compounds represented by the formula(1), particularly preferred are compounds represented by the followingformula (4), having an adamantane skeleton and also having oxetanylgroup or epoxy group, for the easy synthesis and good properties, etc.

In the above formula, R¹ is an alkyl group of 1 to 4 carbon atoms, aperfluoroalkyl group of 1 to 4 carbon atoms, or a fluorine atom; a is aninteger of 0 to 2; and b is an integer of 0 to 2.

Y is a group represented by the following formula (2):

or a group represented by the following formula (3):

In the above formulas, R², R³, R⁵ and R⁶ are each independently ahydrogen atom, a fluorine atom or an alkyl group of 1 to 4 carbon atoms.R⁴ is a methyl group or an ethyl group. p and q are each an integer of 0to 4.

Of the curable adamantane compounds represented by the formula (4),preferred are those curable adamantane compounds wherein both p and qare 0 (zero), for good physical properties, etc. As preferred specificexamples of the compounds, there can be mentioned adamantane compoundshaving oxetanyl group, such as1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane,5,7-dimethyl-1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane,1,3,5-tris[(3-ethyloxetan-3-yl)methoxy]adamantane and the like; andadamantane compounds having epoxy group, such as1,3-bis(glycidyloxy)adamantane,5,7-dimethyl-1,3-bis(glycidyloxy)adamantane,1,3,5-tris(glycidyloxy)adamantane and the like.

Of these compounds, particularly preferred are adamantane compoundshaving oxetanyl group, such as1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane,1,3,5-tris[(3-ethyloxetan-3-yl)methoxy]adamantane and the like, andadamantane compounds having epoxy group, such as1,3-bis(glycidyloxy)adamantane, 1,3,5-tris(glycidyloxymethyl)adamantaneand the like, for the easy production and the high heat resistance ofthe cured material obtained.

As to the process for production of each curable polycyclic compound ofthe present invention, there is no particular restriction. However, itcan be produced preferably by the following processes.

(First Production Process)

(a) In the first production process, a polycyclic hydroxy compoundhaving at least two hydroxyl groups, represented by the followingformula (9):

[wherein A, R¹, n and m have the same definitions as given in theformula (8); R⁷ and R⁸ are each independently a hydrogen atom, afluorine atom or an alkyl group of 1 to 4 carbon atoms; and r is aninteger of 0 to 4] is converted into a metal alcoholate; then, the metalalcoholate is reacted with an oxetane compound or an epoxy compound eachhaving eliminatable group; thereby, a curable polycyclic compound of thepresent invention can be obtained.

With respect to the eliminatable group, there is no particularrestriction as long as it is a group which reacts with an nucleophilicreagent (particularly an alcoholate anion in the present invention) andis eliminated as an anion. As the eliminatable group, there cangenerally be used a halogen atom such as chlorine atom, bromine atom,iodine atom or the like; or, a sulfonyloxy group such asbenzenesulfonyloxy group, p-toluenesulfonyloxy group, p-brominatedbenzenesulfonyloxy group, methanesulfonyloxy group,trifluoromethanesulfonyloxy group or the like.

As specific examples of the raw material compound represented by theformula (9), there can be mentioned 1,3-adamantanediol,2,5-norbornanediol, 2,6-bicyclooctanediol, 2,7-bicyclononanediol,2,7-tetrahydrodicyclopentadienediol, 5-ethyl-1,3-adamantanediol,1-ethyl-2,5-norbornanediol, 1-ethyl-2,6-bicyclooctanediol,1-ethyl-2,7-bicyclononanediol,1-ethyl-2,7-tetrahydrodicyclopentadienediol,5,7-dimethyl-1,3-adamantanediol, 1,4-dimethyl-2,5-norbornanediol,1,5-dimethyl-2,6-bicyclooctanediol, 1,5-dimethyl-2,7-bicyclononanediol,1,5-dimethyl-2,7-tetrahydrodicyclopentadienediol, 1,3,5-adamantanetriol,1,3,6-adamantanetriol, 2,3,5-norbornanetriol, 2,4,6-bicyclooctanetriol,2,4,7-bicyclononanetriol, 2,5,7-tetrahydrodicyclopentadienetriol,7-ethyl-1,3,5-adamantanetriol, 1-ethyl-2,3,5-norbornanetriol,1-ethyl-2,4,6-bicyclooctanetriol, 1-ethyl-2,4,7-bicyclononanetriol,1-ethyl-2,5,7-tetrahydrodicyclopentadienetriol,1,3,5,7-adamantanetetraol, 1,2,3,5-norbornanetetraol,1,2,4,6-bicyclooctanetetraol, 1,2,4,7-bicyclononanetetraol,1,2,5,7-tetrahydrodicyclopentadienetetraol,1,3-bis(hydroxymethyl)adamantane, 2,5-bis(hydroxymethyl)norbornane,2,6-bis(hyroxymethyl)bicyclooctane, 2,7-bis(hydroxymethyl)bicyclononane,2,7-bis(hydroxymethyl)tetrahydrodicyclopentadiene,1,3,5-tris(hydroxymethyl)adamantane,1,3-bis(hydroxyperfluoromethyl)adamantane,2,5-bis(hydroxyperfluoromethyl)norbornane,2,6-bis(hydroxyperfluoromethyl)bicyclooctane,2,7-bis(hydroxyperfluoromethyl)bicyclononane, and2,7-bis(hydroxyperfluoromethyl)tetrahydrodicyclopentadiene.

The polycyclic hydroxy compound represented by the formula (9), when theA of the formula (9) is a group derived form adamantane, can be producedeasily by a method of oxidizing adamantane or an alkyladamantane.

Or, the compound of the formula (9) can be obtained easily byhydrolyzing a halogenated adamantane.

As the above-mentioned method for oxidation, there can be employed, forexample, an oxidation method using chromic acid, disclosed in JP1967-16621 A and JP 1990-104553 A; an oxidation method using a rutheniumcompound and a hypochlorite, disclosed in JP 2000-219646 A and JP2001-26563 A; and an oxidation method using hydroxyphthalimide as acatalyst, disclosed in JP 1996-38909 A or JP 1997-327626 A and JP1998-286467 A.

As the above-mentioned method for hydrolysis, there can be employed, forexample, a method for hydrolysis of brominated adamantane, disclosed inJP 1990-196744 A and JP 1991-118342 A.

When, the A of the formula (9) is a group derived from norbornane,bicyclooctane, bicyclononane or tetrahydrodicyclopentadiene, an alcoholcompound can be synthesized by using, as a raw material, norbornene,bicyclooctene, bicyclononene or dicyclopentadiene and subjecting it toacid catalyzed addition of water, as described in Stand undEntwicklungstendenzen in der Chemie der Epoxydharze, Kunststoffe, Nos. 3& 4, 1967.

When p is 1 to 4, there is a method which comprises reacting apolycyclic hydrocarbon compound such as adamantane with a borontrifluoride-ether complex and fuming sulfuric acid in 95% concentratedsulfuric acid to give rise to dicarboxylation and then reducing thedicarboxylation product with a reducing agent such as lithium aluminumhydride, as described in Journal of Medicinal Chemistry, Vol. 18, No. 7(1975).

Or, the alcohol compound can be easily obtained by reacting a polycyclichydrocarbon compound (e.g. adamantane) with vinyl chloride, sulfuricanhydride and concentrated nitric acid in concentrated sulfuric acid togive rise to dimethylcarboxylation and then reducing thedimethylcarboxylation product with a reducing agent (e.g. lithiumaluminum hydride), as described in Izvestia Akademii Nauk, SeriyaKhimicheskaya, No. 7, pp. 1612 to 1615 (1992).

As the oxetane compound having eliminatable group, which is reacted withthe metal alcoholate of the polycyclic hydroxy compound of the formula(9), there can be mentioned, for example, p-toluenesulfonic acid esterof 3-alkyl-3-hydroxymethyloxetane. The synthesis method of this oxetanecompound is disclosed in Spanish Patent No. 2073995. Specificallyexplaining, the oxetane compound can be easily synthesized by reacting a3-alkyl-3-hydroxymethyloxetane with a sulfonyl chloride compoundrepresented by RSO₂Cl (wherein R is, for example, a p-tolyl group) inthe presence of an appropriate basic compound (e.g. pyridine) in anorganic solvent at 0° C. to room temperature (25° C.).

As the epoxy compound having eliminatable group, there can be mentioned,for example, epichlorohydrin and epibromohydrin.

The alcoholate of the polycyclic hydroxy compound represented by theformula (9) can be produced by reacting the compound with a basiccompound in a solvent. As the basic compound, there is ordinarily usedan alkali metal, an alkaline earth metal or an organometal compoundcontaining such a metal (such a metal or compound is hereinafterreferred to as alkali metal or the like). As the alkali metal or thelike, there can be mentioned alkali metals such as sodium and the like;alkali metal hydrides such as sodium hydride and the like; alkali metalhydroxides such as sodium hydroxide, potassium hydroxide and the like;alkaline earth metals such as magnesium, calcium and the like;organometal compounds such as methyllithium, butyllithium and the like;and so forth.

The use amount of the basic compound is appropriately determineddepending upon the number of m of the formula (9). Ordinarily, the useamount is preferably 0.5 to 5.0 mols, particularly preferably 1.0 to 1.5mols relative to 1 mol of the hydroxyl group contained in the polycyclichydroxy compound represented by the formula (9).

As the solvent used in the above reaction, there can be mentioned, forexample, aromatic hydrocarbon solvents such as toluene, xylene and thelike; and aprotic polar solvents such as tetrahydrofuran,N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide,hexamethylphosphoric triamide, N-methylpyrrolidone and the like.

As to the use amount of the solvent, there is no particular restriction.However, too small an amount results in reduced reactivity and too largean amount is not preferred for economy; therefore, the solvent is usedin an amount of 1 to 500 mols, preferably 2 to 300 mols relative to 1mol of hydroxyl group of the polycyclic hydroxy compound.

As to the reaction temperature, there is no particular restriction.However, when there is used an alkali metal or an alkali metal hydrideas the basic compound, the temperature is preferably 0 to 80° C. and,when there is used an alkali metal hydroxide, the temperature ispreferably 30 to 130° C. The reaction time differs depending upon thereaction temperature used, but is ordinarily about 1 to 10 hours.

After the polycyclic hydroxy compound has been converted into analcoholate, there is added thereto an oxetane compound havingeliminatable group or an epoxy compound having eliminatable group,whereby a curable polycyclic compound of the present invention can beobtained. In this case, the use amount of the oxetane compound havingeliminatable group or the epoxy compound having eliminatable group maybe appropriately determined depending upon the number of the m of thepolycyclic hydroxy compound represented by the formula (9) to beproduced. Ordinarily, the use amount is preferred to be 0.5 to 5.0 mols,particularly 1.0 to 1.5 mols relative to 1 mol of the hydroxyl groupcontained in the polycyclic compound represented by the formula (9).

The temperature of the above reaction is not particularly restricted butis preferred to be 0 to 130° C. The reaction may be conducted by using apressure apparatus (e.g. an autoclave), as necessary. The reaction timediffers depending upon the reaction temperature used but is ordinarilyabout 1 to 48 hours. An additive such as potassium iodide or the likemay be used for a increased reaction rate.

After the above reaction, the reaction mixture is neutralized with anacid such as hydrochloric acid or the like and then a purificationtreatment is conducted as necessary, whereby a curable polycycliccompound (1) of the present invention can be obtained.

(Second Production Process)

A polycyclic epoxy compound, which is a curable polycyclic compound ofthe general formula (1) wherein Y is a group represented by the formula(3), can be obtained by converting a polycyclic hydroxy compoundrepresented by the general formula (9) into an alcoholate, reacting thealcoholate with an allyl compound having eliminatable group, andallowing an oxidizing agent to act on the reaction product.

This second production process is described in more detail. In thisprocess, a polycyclic epoxy compound represented by the followingformula (8) is produced.

In the formula (8), A, R¹, n and m have the same definitions as in thegeneral formula (1).

In the formula (8), Z is the following group represented by theabove-shown formula (3).

The process for producing the compound of the formula (8) comprises thefollowing steps (a) to (c). In this process, a novel polycyclic allylcompound produced in the steps (a) and (b) is used as an intermediate,whereby an intended product (8) can be obtained easily at a high yieldat a high purity. The steps (a) to (c) are explained in detail below.

In the production process of the present invention, first in the step(a), a polycyclic hydroxy compound represented by the following formula(9) is reacted with a basic compound, preferably an alkali metal, analkaline earth metal or an organometal compound containing such a metal,to obtain an alcoholate.

This step is conducted according to the same manner as in the firstproduction process.

In the formula (9), A, R¹, n and m have the same definitions as in theformula (8); R⁷ and R⁸ are each independently a hydrogen atom, afluorine atom or an alkyl group of 1 to 4 carbon atoms; and r is aninteger of 0 to 4.

In the present process, in the step (b), the alcoholate of a polycyclichydroxy compound, obtained in the step (a) is reacted with an allylgroup-containing compound represented by the following formula (10) toobtain a polycyclic allyl compound represented by the following formula(11).

In the formula (10), X is a halogen atom or a sulfonyloxy group. In theformula (11), A, R¹, n and m have the same definitions as in the formula(8); and W is a group represented by the following formula (12).

{wherein R⁵, R⁶ and q have the same definitions as in the formula (3)}.

As the allyl group-containing compound represented by the formula (10),there can be used a reagent or an easily obtainable industrial rawmaterial with no restriction. As specific examples thereof, there can bementioned vinyl chloride, vinyl bromide, vinyl iodide, allyl chloride,allyl bromide, allyl iodide, allyl benzenesulfonate, allyltrifluoromethanesulfonate, allyl toluenesulfonate, allyl brominatedbenzenesulfonate, allyl methanesulfonate. Allyl chloride, allyl bromideand allyl iodide are used preferably in view of the availability,operability, reactivity, etc. The use amount of the allylgroup-containing compound is 1 mole relative to 1 mol of the hydroxylgroup contained in the polycyclic hydroxy compound (9) which is a rawmaterial for alcoholate; however, in view of the hindrance by theremaining basic compound, etc., the amount is preferably 1.0 to 5.0mols, more preferably 1.05 to 3.0 mols. As the method for contacting thealcoholate of the polycyclic hydroxy compound (9) with the allylgroup-containing compound (10), there is preferred, in view of the heatgenerated, etc., a method of dropping the allyl group-containingcompound into the alcoholate of the polycyclic hydroxy compound, or amethod of dropping the alcoholate of the polycyclic hydroxy compound (9)into the allyl group-containing compound (10). That is, there ispreferred a method of dropping either one raw material to the other rawmaterial. There is no particular restriction as to the temperatureduring dropping. However, too high a dropping temperature produces alarge amount of impurity, and too low a dropping temperature results ina reduced reaction rate. The dropping temperature is ordinarily −40 to100° C., preferably −30 to 90° C. The time of the reaction differsdepending upon the reaction temperature employed but is ordinarily about0.5 to 10 hours from the completion of dropping.

The above-obtained polycyclic allyl compound is washed with water, thensubjected to an operation such as solvent removal by distillation and isrecovered as a crude polycyclic ally compound of a liquid state. Thiscrude compound may be used per se but is preferred to be purified bydistillation, silica gel column chromatography or the like.

The polycyclic allyl compound obtained is a compound (an intermediate)which is a direct raw material for intended polycyclic epoxy compound.The difference between the intermediate and the intended compound issimply that the group -Z in the formula (8) has been changed to a group—W (specifically explaining, epoxy group (as the group Z) has beenchanged to vinyl group). Therefore, the A, R¹, R⁵, R⁶, m, n and q in thepolycyclic allyl compound are the same as in the formula (8).

As preferred specific examples of the polycyclic allyl compoundrepresented by the formula (11), there can be mentioned1,3-bis(2-propenyloxy)adamantane, 2,5-bis(2-propenyloxy)norbornane,2,6-bis(2-propenyloxy)bicyclooctane,2,7-bis(2-propenyloxy)bicyclononane,2,7-bis(2-propenyloxy)tetrahydrodicyclopentadiene,5,7-dimethyl-1,3-bis(2-propenyloxy)adamantane,1,4-dimethyl-2,5-bis(2-propenyloxy)norbornane,1,5-dimethyl-2,6-bis(2-propenyloxy)bicyclooctane,1,5-dimethyl-2,7-bis(2-propenyloxy)bicyclononane,1,5-dimethyl-2,7-bis(2-propenyloxy)tetrahydrodicyclopentadiene,1,3,5-tris(2-propenyloxy)adamantane,2,3,5-tris(2-propenyloxy)norbornane,2,4,6-tris(2-propenyloxy)bicyclooctane,2,4,7-tris(2-propenyloxy)bicyclononane,2,5,7-tris(2-propenyloxy)tetrahydrodicyclopentadiene,1,3-bis(2-propeneyloxymethyl)adamantane,2,5-bis(2-propeneyloxymethyl)norbornane,2,6-bis(2-propeneyloxymethyl)bicyclooctane,2,7-bis(2-propeneyloxymethyl)bicyclononane,2,7-bis(2-propeneyloxymethyl)tetrahydrodicyclopentadiene,1,3,5-tris(2-propenyloxymethyl)adamantane,2,3,5-tris(2-propenyloxymethyl)norbornane,2,4,6-tris(2-propenyloxymethyl)bicyclooctane,2,4,7-tris(2-propenyloxymethyl)bicyclononane, and2,5,7-tris(2-propenyloxymethyl)tetrahydrodicyclopentadiene.

In the present process, in the step (c), the polycyclic allyl compoundis oxidized to convert the vinyl group (the group —W) into epoxy group(group -Z), whereby an intended polycyclic epoxy compound is obtained.

The oxidation includes oxidation by organic peroxide (e.g. peracid suchas peracetic acid, perbenzoic acid, m-chloroperbenzoic acid or the like,or peroxide such as dimethyldioxirane or the like) in solvent, oxidationby oxygen and oxidation by chromic acid. The oxidation by organicperoxide is simple in view of the conversion and the non-use ofcatalyst. Of the above organic peroxides, m-chloroperbenzoic acid isparticularly preferable in view of the availability and safety. The useamount of the organic peroxide is 1 mol relative to 1 mol of the allylgroup contained in the polycyclic allyl compound, but is ordinarily 1 to5 mols, preferably 1.05 to 3.0 mols. As the solvent used in the abovereaction, there are mentioned halogenated solvents such asdichloromethane, chloroform, carbon tetrachloride and the like;aliphatic hydrocarbon solvents such as hexane, heptane, cyclohexane andthe like; aromatic hydrocarbon solvents such as toluene, xylene and thelike; and so forth. There is no particular restriction as to the useamount of the solvent. However, too small an amount results in reducedreactivity and too large an amount is uneconomical; therefore, thesolvent is used in an amount of 1 to 500 times, preferably 2 to 300times the mass of the polycyclic allyl compound used. The temperature ofthe reaction is not restricted particularly. However, too high atemperature results in an increased amount of impurity and too low atemperature results in a reduced reaction rate. Hence, the temperatureis ordinarily −10 to 100° C., preferably 0 to 60° C. The reaction timediffers depending upon the reaction temperature employed and the useamount of organic peroxide, but is ordinarily about 5 to 100 hours.

The above-obtained polycyclic epoxy compound (8) is subjected to washingwith water and distillation for solvent removal. The resulting crudepolycyclic epoxy compound has a high purity per se, but is subjected topurification by distillation, silica gel column chromatography or thelike to obtain a polycyclic epoxy compound of higher purity.

The curable polycyclic compound (1) of the present invention has apolycyclic hydrocarbon skeleton and accordingly gives a cured materialhaving superior optical properties and heat resistance. Further, thecurable polycyclic compound (1) of the present invention containsoxetane group or epoxy group introduced into the polycyclic hydrocarbonskeleton and accordingly has a feature of showing a small shrinkageduring the polymerization. Therefore, the curable polycyclic compound(1) of the present invention is suitably used particularly in theencapsulant for light-emitting diode.

In JP 2003-73452 A, it is described that, when bisphenol A orhydrogenated bisphenol A is reacted with epichlorohydrin to produce abisphenol A type epoxy resin or a hydrogenated bisphenol A type epoxyresin, the amount of chlorine remaining in the produced resin reaches50,000 ppm.

When a curable polycyclic compound contains a large amount of halogenmolecule or halogen ion, the resin obtained by curing the compound isextremely low in heat resistance and light resistance.

Accordingly, when a curable polycyclic compound containing a largeamount of halogen molecule or halogen ion is used in applications suchas encapsulant and the like, the resin formed causes deterioration andcan not be used stably.

In the curable polycyclic compound of the present invention, the halogenmolecule or halogen ion contained therein as an impurity can be reducedto a low level of 100 to 2,000 ppm, preferably 200 to 2,000 ppm byselecting the production conditions and conducting purification.Therefore, the curable polycyclic compound of the present invention issuited for applications requiring heat resistance and weatherresistance, such as encapsulant and the like.

In order to analyze the halogen molecule or halogen ion contained as animpurity in the curable polycyclic compound of the present invention, aknown method can be employed. As the method, there can be mentioned, forexample, a quantitative analysis method of organic chlorine (aquantitative analysis method of saponifiable chlorine by ISO 4583) and aquantitative analysis method of inorganic chlorine (a method by ISO4573).

The curable polycyclic compound of the present invention can be usedsuitably, for example, as a raw material for various plastic substrates,a raw material for coating, a raw material for adhesive and a rawmaterial for encapsulant. The curable polycyclic compound, whensubjected to homopolymerization, gives a cured material wherein theabove-mentioned properties of the compound are utilized.

It is possible that the curable polycyclic compound of the presentinvention is mixed with other curable compound reactive therewith(hereinafter, referred to as co-reacting agent) and the resultingcurable mixture is subjected to co-polymerization to obtain a curedmaterial.

There is no particular restriction as to the co-reacting agent as longas it is reactive with the curable polycyclic compound of the presentinvention. As the co-reacting agent, there may be appropriately selecteda co-reacting agent which can allow a cured material obtained to haveproperties required in an intended application. As such a co-reactingagent, there can be mentioned oxetane compounds, epoxy compounds andcation-polymerizable monomers. As specific examples, there can bementioned oxetane compounds such as xylylenedioxetane,3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane and thelike; bisphenol A type epoxy compounds such as bisphenol A diglycidylether and the like; bisphenol F type epoxy compounds such as bisphenol Fdiglycidyl ether and the like; hydrogenated bisphenol A type epoxycompounds such as hydrogenated bisphenol A diglycidyl ether and thelike; epoxy compounds such as phenolic novolac type epoxy compound,glycidylamine type epoxy compound, naphthalene type epoxy compound,silicon type epoxy compound and the like; and cation-polymerizablemonomers such as isobutyl vinyl ether, N-vinylcarbazole,p-methoxystyrene, isobutene and the like. These co-reacting agents canbe used singly or in admixture of two or more kinds.

The composition of the curable mixture may be determined appropriatelydepending upon the application purpose. When the curable polycycliccompound is used for property improvement, the curable polycycliccompound is used in an amount of preferably 10 to 98% by mass,particularly preferably 20 to 95% by mass (the rest is the co-reactingagent) based on the total mass of the curable mixture obtained.

(Curing Agent)

There is no particular restriction as to the method for curing thecurable polycyclic compound or the curable mixture between the compoundand the co-reacting agent to obtain a cured material. There can beemployed a known method.

The curable polycyclic compound or the curable mixture is mixed, asnecessary, with various additives and stabilizers such as filler,coupling agent, flame retardant, ultraviolet absorber, infraredabsorber, ultraviolet stabilizer, antioxidant, coloring inhibitor,antistatic agent, dye, pigment, perfume and the like, and then can bemade into a cured material. The addition amount of such additives andstabilizers is determined by an ordinary method.

The curable polycyclic compound having oxetanyl group can be cured bycationic polymerization, using a curing agent as necessary.

The curable polycyclic compound having epoxy group can be cured bycationic polymerization, anionic polymerization or the like, using acuring agent as necessary. Here, the curing agent means a compound whichhas a functional group chemically reacting with oxetanyl group or epoxygroup and which reacts with a compound having oxetanyl group or epoxygroup to form a cured material.

As the curing agent, there can be used, with no restriction, compoundsordinarily used in curing of oxetanyl compound or epoxy compound. Therecan be mentioned, for example, phenol derivatives such as bisphenol A,bisphenol F, novolac resin and the like; acid anhydrides such asphthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride,pyromellitic anhydride, 3-methyltetrahydrophthalic anhydride and thelike; amine compounds such as m-phenylenediamine, diethylenetriamine,triethylenetetramine, xylenediamine, diaminodiphenylmethane and thelike; and polyamides. Of these compounds, acid anhydrides areparticularly preferable.

The preferred use amount of the curing agent is such an amount that thefunctional group of curing agent reacting with the oxetanyl group orepoxy group of curable polycyclic compound becomes 0.6 to 1.5 mols,preferably 0.8 to 1.2 mols per 1 mol of the oxetanyl group or epoxygroup. When the proportion of the functional group of curing agent tothe oxetanyl group or epoxy group is less than 0.6 or more than 1.4, thecured material obtained tends to be low in strength and waterresistance.

As the cationic polymerization initiator, there can be used, with norestriction, those ordinarily used in curing of a compound havingoxetanyl group or epoxy group. There can be mentioned, for example,protonic acids such as trifluoroacetic acid, trifluoromethanesulfonicacid, chlorosulfonic acid and the like; initiators selected fromcombinations of Lewis acid (e.g. boron trifluoride, tin tetrachloride,iron chloride, phosphorus pentafluoride, arsenic pentafluoride orantimony pentafluoride) and cation source (e.g. protonic acid, water oralcohol); cation-forming substances such as iodine and the like; andcationic photo-initiators such as diaryl iodonium salt (e.g. diphenyliodonium hexafluorophosphate), triaryl sulfonium salt (e.g. triphenylsulfonium hexafluorophosphate) and the like. The use amount of thecationic initiator is preferably 0.01 to 10 mols, more preferably 0.2 to5 mols per 1 mol of the oxetanyl group or epoxy group of curablepolycyclic compound.

As the anionic polymerization initiator, there can be used, with norestriction, those ordinarily used in curing of an epoxy compound. Therecan be mentioned, for example, tertiary amines such asdibutylmethylamine, diundecylmethylamine and the like. The use amount ofthe anionic polymerization initiator is such that the functional groupof polymerization initiator reacting with the epoxy group of the curablepolycyclic compound of the present invention becomes 0.01 to 10 mols,more preferably 0.2 to 5 mols per 1 mol of the epoxy group.

The curing agent may contain components other than mentioned above. Thecuring agent is preferred to contain a curing accelerator from thestandpoint of, in particular, rapid formation of cured material. Thecuring accelerator is particularly effective when used in combinationwith the curing agent. As the curing accelerator, there can bementioned, for example, tertiary amines such as triethylamine,tributylamine, pyridine, benzyldimethylamine,1,8-diazabicyclo[5.4.0]undecene-7 and the like; organic acid saltsthereof; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazoleand the like; organic acid salts thereof; metal salts of organic acids,such as tin octylate and the like; amine salt of boron trifluoride; andquaternary phosphoric acid salts. Of these, preferably used from thestandpoint of light resistance are quaternary phosphoric acid salts suchas tetrabutylphosphonium diethylphosphorodithioate and the like. Thepreferred use amount of the curing accelerator is 0.1 to 5 parts by massper 100 parts by mass of the curable polycyclic compound.

In the present invention, particularly preferred as the curablecomposition is, as described later, a composition which contains, as acurable polycyclic compound, a compound represented by theabove-mentioned formula (4) wherein Y is a group represented by theformula (3), that is, an epoxy group-containing adamantane compound.

Description is made below on the specific form of a curable compositionusing such an epoxy group-containing adamantane compound.

The curable composition may contain an epoxy compound other than theepoxy group-containing adamantane compound (hereinafter, referred to asother epoxy compound), for improvement in adhesivity, electricalproperties, workability for production, etc. As the other epoxycompound, there can be used a known epoxy compound with no restriction.As examples of preferably usable other epoxy compound, there can bementioned phenol type glycidyl ethers such as bisphenol A glycidylether, brominated bisphenol A glycidyl ether, bisphenol C glycidylether, tetraglycidyl benzophenone, diglycidyl bisphenol F,triglycidyl-p-aminophenol, novolac type epoxy and the like; alicyclicglycidyl ethers such as diglycidyl cyclohexane-1,3-dicarboxylate,hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol Aglycidyl ether and the like; alicyclic epoxys such as vinylcyclohexenedioxide,7-oxabicyclo[4.1.0]hept-3-ylmethyl-7-oxabicyclo[4.1.0]heptane-3-carboxylateand the like; and glycidyl esters such as diglycidyl phthalate,diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, glycidyldimerate, diglycidyl hexahydrophthalate, diglycidyl p-oxybenzoate andthe like.

Of these other epoxy compounds, preferred are alicyclic epoxy compoundsfor the good light resistance. As examples of such alicyclic epoxycompounds, there can be mentioned alicyclic glycidyl ethers such ashydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol Aglycidyl ether and the like; and alicyclic epoxys such asvinylcyclohexene dioxide,7-oxabicyclo[4.1.0]hept-3-ylmethyl-7-oxabicyclo[4.1.0]heptane-3-carboxylateand the like. Particularly preferred are alicyclic epoxys having3,4-epoxycyclohexyl group. As an example thereof, there can be mentioned7-oxabicyclo[4.1.0]hept-3-ylmethyl-7-oxabicyclo[4.1.0]heptane-3-carboxylate.

As to the content of the other epoxy compound, there is no particularrestriction. However, the use amount is preferably 1 to 1,000 parts bymass relative to 100 parts by mass of the epoxy group-containingadamantane compound from the standpoint of good light resistance andheat resistance.

The curable composition can further contain, as necessary, a siliconecompound (e.g. polydimethylsiloxane or polyphenylmethylsiloxane), afiller (e.g. calcium carbonate or magnesium oxide), a surfactant, aleveling agent, an anti-static agent, a light or heat stabilizer (e.g.ultraviolet absorber, anti-oxidant, hindered amine or hindered phenol),etc. for improved properties of cured material. The use amount of theseadditives is not restricted particularly but is preferably 1 to 1,000parts by mass, particularly preferably 20 to 500 parts by mass relativeto 100 parts by mass of the total amount of the epoxy group-containingadamantane compound and the other epoxy compound.

(Curable Composition)

Description is made below on a curable composition superior particularlyas an encapsulant for LED device.

This curable composition is obtained by mixing a curable polycycliccompound (including an oligomer described later) of the presentinvention, preferably an epoxy group-containing adamantane compound, acuring agent and, as necessary, various optional components mentionedabove. With respect to the mixing method therefor, when the curablepolycyclic compound is an epoxy group-containing adamantane compound, itis generally preferred that the epoxy group-containing adamantanecompound, a curing agent and optional components other than cationicpolymerization initiator are mixed uniformly and lastly a cationicpolymerization initiator is added, followed by uniform mixing.

The composition obtained is maintained under reduced pressure to giverise to defoaming, in order to allow the cured material obtained to havehigher transparency.

The curable composition has a feature of being superior in lightresistance, heat resistance, etc. and accordingly is usable preferablyas an encapsulant for LED device. There is no particular restriction asto the method for using the curable composition in encapsulation of LEDdevice. In general, there is mentioned a method which comprises bondinga LED device to a package by die bonding, inserting a pair of lead wiresextending from the package, into the LED device to fix the LED device inthe plastic-made package, pouring a curable composition of the presentinvention into the package, then curing the composition by heat orlight, to conduct encapsulation.

For curing the composition by heat, there are, for example, a method ofallowing the composition to stand in a heating oven for a given time anda method of mounting the composition on a belt conveyor or the like andpassing it through a heating zone (e.g. on a plate heater). When thecomposition is used as an encapsulant for LED device and cured, theheating temperature is not particularly restricted as long as the LEDdevice is not damaged at the temperature; however, the temperature ispreferably 20 to 250° C., more preferably 80 to 200° C. The heating timeis preferably 5 minutes to 48 hours. When the composition is cured bylight, there can be used a known light source such as high-pressuremercury lamp, low-pressure mercury lamp, a metal halide lamp, a halogenlamp or the like. In that case, the light source, the irradiation doseand the irradiation time may be appropriately selected depending uponthe composition of the curable composition used.

(Oligomer)

A high-quality cured material can be formed not only by the curablepolycyclic compound of the present invention but also by a compoundhaving a structure in which two to four molecules (these molecules maybe the same or different) of the curable polycyclic compound of thepresent invention are polymerized or condensed as described below (sincethis compound can be seen as a dimer or tetramer, it is hereinafterreferred to also as oligomer). The oligomer can be preferably used as araw material for various plastic substrates, a raw material for coating,a raw material for adhesive, a raw material for encapsulant, etc.

The oligomer can be easily produced generally by a fusion method, anadvanced method, a method which is called a two-step reaction method, orthe following method wherein a monomer (a starting raw material) and analcohol are subjected to addition polymerization. That is, the oligomercan be obtained by reacting a polycyclic hydroxy compound having atleast two hydroxyl groups, represented by the following formula (9):

{wherein A, R¹, n and m have the same definitions as in the formula (8);R⁷ and R⁸ are each independently a hydrogen atom, a fluorine atom or analkyl group of 1 to 4 carbon atoms; and r is an integer of 0 to 4} witha basic compound and an oxetane compound or an epoxy compound eachhaving eliminatable group, simultaneously.

As the basic compound, there can be mentioned, for example, alkalimetals such as sodium and the like; alkali metal hydrides such as sodiumhydride and the like; and alkali metal hydroxides such as sodiumhydroxide, potassium hydroxide and the like. The use amount of the basiccompound is not particularly restricted; however, it is preferably 1.0to 5.0 mols, particularly preferably 1.5 to 3.0 mols per 1 mol of thehydroxyl group contained in the polycyclic hydrocarbon compoundrepresented by the formula (9).

The oxetane compound having eliminatable group can be exemplified by3-alkyl-3-hydroxymethyloxetane p-toluenesulfonate. The synthesis methodfor the compound is disclosed in Spanish Patent No. 2073995.

Specifically explaining, the compound can be synthesized easily byreacting a 3-alkyl-3-hydroxymethyloxetane with a sulfonyl chloridecompound represented by RSO₂Cl (R is p-tolyl group or the like) in thepresence of an appropriate basic compound (e.g. pyridine) in an organicsolvent at 0° C. to room temperature (25° C.).

As the epoxy compound having eliminatable group, there can be mentioned,for example, epichlorohydrin and epibromohydrin.

As the solvent used in the above reaction, there can be mentioned, forexample, aromatic hydrocarbon solvents such as toluene, xylene and thelike; and aprotic polar solvents such as tetrahydrofuran,N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide,hexamethylphosphoric triamide, N-methylpyrrolidone and the like.

In the above reaction, there are simultaneously added the compound ofthe formula (9), the basic compound, the oxetane compound or the epoxycompound each having eliminatable group and the solvent.

The reaction temperature is not particularly restricted but ispreferably 0 to 130° C. The reaction may be conducted by using, asnecessary, a pressure apparatus (e.g. an autoclave).

The reaction time differs depending upon the reaction temperature usedbut is ordinarily preferred to be about 1 to 48 hours. An additive suchas potassium iodide or the like may be added for increased reactionrate.

After the completion of the reaction, the reaction mixture isneutralized with hydrochloric acid or the like and subjected to apurification treatment, whereby the above-mentioned oligomer can beobtained.

Examples of the general formula of the oligomer are shown by thefollowing formula (6) and (7).

{wherein A, R¹, R², R³, n and p have the same definitions as in theformula (1); and s is an integer of 1 to 3.}

{wherein A, R¹, R⁵, R⁶, n and q have the same definitions as in theformula (1); and s′ is an integer of 1 to 3.}

As preferable examples of the oligomer, there can be mentioned thefollowings.

(in the above formulas, s is an integer of 1 to 3.)

EXAMPLES

The present invention is specifically described below by way ofExamples. However, the present invention is in no way restricted tothese Examples.

Example 1 Synthesis of 1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane

300 ml of dehydrated tetrahydrofuran containing 16.8 g (0.1 mol) of1,3-adamantanediol and 5.3 g (0.22 mol) of sodium hydride was stirred ina nitrogen atmosphere at the reflux temperature for 2 hours. Thereto wasdropwise added 56.4 g (0.22 mol) of3-ethyl-3-p-toluenesulfonyloxymethyloxetane. 36.5 g (0.22 mol) ofpotassium iodide was added. The resulting mixture was stirred at thereflux temperature for 12 hours. To the reaction mixture was added 200ml of chloroform. The mixture was washed with water, and the chloroformlayer was dried with magnesium sulfate.

The dried chloroform layer was subjected to distillation under reducedpressure for solvent removal, whereby was obtained a white solid andoily matter. This was purified by silica gel column chromatography toobtain 2.39 g (yield: 7.1%) of a white solid and oily matter. Thiscompound was subjected to MASS spectrometry, ¹H-NMR spectrometry andelemental analysis. From the results of the analyses, the compound wasconfirmed to be intended 1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane.The results of analyses are shown below.

MASS (EI): molecular weight 336 (M⁺)

¹H-NMR (TMS standard): δ 1.1-2.0 (m, 20H), 2.6-4.1 (m, 12H)

Elemental analysis: as C₂₀H₃₂O₄

Calculated: C 71.39, H 9.59

Measured: C 71.76, H 9.63

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 210 ppm, the inorganic chlorine content was 10 ppmand the total chlorine content was 220 ppm.

Example 2 Synthesis of 2,5-bis[(3-ethyloxetan-3-yl)methoxy]norbornane

300 ml of dehydrated tetrahydrofuran containing 12.8 g (0.1 mol) of2,5-norbornanediol and 5.3 g (0.22 mol) of sodium hydride was stirred ina nitrogen atmosphere at the reflux temperature for 2 hours. Thereto wasdropwise added 56.4 g (0.22 mol) of3-ethyl-3-p-toluenesulfonyloxymethyloxetane. 36.5 g (0.22 mol) ofpotassium iodide was added. The resulting mixture was stirred at thereflux temperature for 12 hours. To the reaction mixture was added 200ml of chloroform. The chloroform layer was washed with water and thendried with magnesium sulfate. The dried chloroform layer was subjectedto distillation under reduced pressure for solvent removal, whereby wasobtained a white solid and oily matter. This was purified by silica gelcolumn chromatography to obtain 1.39 g (yield: 4.71%) of a white solidand oily matter. This compound was subjected to MASS spectrometry,¹H-NMR spectrometry and elemental analysis. From the results of theanalyses, the compound was confirmed to be intended2,5-bis[(3-ethyloxetan-3-yl)methoxy]norbornane. The results of analysesare shown below.

MASS (EI): molecular weight 296 (M⁺)

¹H-NMR (TMS standard): δ 1.1-2.0 (m, 16H), 2.6-4.1 (m, 12H)

Elemental analysis: as C₁₇H₂₈O₄

Calculated: C 68.89, H 9.52

Measured: C 68.81, H 9.62

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 230 ppm, the inorganic chlorine content was 19 ppmand the total chlorine content was 249 ppm.

Example 3 Synthesis of5,7-dimethyl-1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane

An operation was conducted in the same manner as in Example 1 exceptthat 16.8 g (0.10 mol) of 1,3-adamantanediol was replaced by 19.6 g(0.10 mol) of 5,7-dimethyl-1,3-adamantanediol, whereby was obtained 2.70g (yield: 7.4%) of a white compound and oily matter. This compound wassubjected to MASS spectrometry, ¹H-NMR spectrometry and elementalanalysis. From the results of the analyses, the compound was confirmedto be intended5,7-dimethyl-1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane. The resultsof analyses are shown below.

MASS (EI): molecular weight 364 (M⁺)

¹H-NMR: δ 1.1-2.0 (m, 24H), 2.6-4.1 (m, 12H)

Elemental analysis: as C₂₂H₃₆O₄

Calculated: C 72.49, H 9.95

Measured: C 72.87, H 9.88

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 410 ppm, the inorganic chlorine content was 28 ppmand the total chlorine content was 438 ppm.

Example 4 Synthesis of 1,3,5-tris[(3-ethyloxetan-3-yl)methoxy]adamantane

An operation was conducted in the same manner as in Example 1 exceptthat 16.8 g (0.10 mol) of 1,3-adamantanediol was replaced by 18.4 g(0.10 mol) of 1,3,5-adamantanetriol, the amount of sodium hydride waschanged to 7.9 g (0.33 mol) and the amount of3-ethyl-3-p-toluenesulfonyloxymethyloxetane was changed to 84.6 g (0.33mol), whereby was obtained 1.92 g (yield: 4.4%) of a white compound andoily matter.

This compound was subjected to MASS spectrometry, ¹H-NMR spectrometryand elemental analysis. As a result, the compound was confirmed to beintended 1,3,5-tri[(3-ethyloxetan-3-yl)methoxy]adamantane.

The results of analyses are shown below.

MASS (EI): molecular weight 436 (M⁺)

¹H-NMR: δ 1.1-2.0 (m, 32H), 2.6-4.1 (m, 18H)

Elemental analysis: as C₂₅H₄₀O₆

Calculated: C 68.78, H 9.23

Measured: C 68.56, H 9.54

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 360 ppm, the inorganic chlorine content was 40 ppmand the total chlorine content was 400 ppm.

Example 5 Synthesis of 1,3-bis(glycidyloxy)adamantane

300 ml of dehydrated tetrahydrofuran containing 16.8 g (0.1 mol) of1,3-adamantanediol and 5.3 g (0.22 mol) of sodium hydride was stirred ina nitrogen atmosphere at the reflux temperature for 2 hours. Thereto wasdropwise added 20.4 g (0.22 mol) of epichlorohydrin, followed bystirring at the reflux temperature for 12 hours. To the reaction mixturewas added 200 ml of chloroform. The chloroform layer was washed withwater and dried with magnesium sulfate. The dried chloroform layer wassubjected to distillation under reduced pressure for solvent removal, toobtain oily matter. It was purified by silica gel column chromatographyto obtain 1.79 g (yield: 6.4%) of oily matter.

This compound was subjected to MASS spectrometry, ¹H-NMR spectrometryand elemental analysis. As a result, the compound was confirmed to beintended 1,3-bis(glycidyloxy)adamantane. The results of analyses areshown below.

MASS (EI): molecular weight 280 (M⁺)

¹H-NMR: δ 1.1-2.5 (m, 14H), 2.5-4.1 (m, 10H)

Elemental analysis: as C₁₆H₂₄O₄

Calculated: C 68.54, H 8.63

Measured: C 68.22, H 8.85

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 600 ppm, the inorganic chlorine content was 10 ppmand the total chlorine content was 610 ppm.

Example 6 Synthesis of 2,5-bis(glycidyloxy)norbornane

300 ml of dehydrated tetrahydrofuran containing 12.8 g (0.1 mol) of2,5-norbrnanediol and 5.3 g (0.22 mol) of sodium hydride was stirred ina nitrogen atmosphere at the reflux temperature for 2 hours. Thereto wasdropwise added 20.4 g (0.22 mol) of epichlorohydrin, followed bystirring at the reflux temperature for 12 hours. To the reaction mixturewas added 200 ml of chloroform. The chloroform layer was washed withwater and dried with magnesium sulfate. The dried chloroform layer wassubjected to distillation under reduced pressure for solvent removal,whereby was obtained a white solid and oily matter. This was purified bysilica gel column chromatography to obtain 1.20 g (yield: 5.0%) of awhite solid and oily matter. This compound was subjected to MASSspectrometry, ¹H-NMR spectrometry and elemental analysis. From theresults of the analyses, the compound was confirmed to be intended2,5-bis(glycidyloxy)norbornane. The results of analyses are shown below.

MASS (EI): molecular weight 240 (M⁺)

¹H-NMR: δ 1.1-2.0 (m, 10H), 2.7-4.1 (m, 10H)

Elemental analysis: as C₁₃H₂₀O₄

Calculated: C 64.98, H 8.39

Measured: C 64.92, H 8.40

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 530 ppm, the inorganic chlorine content was 27 ppmand the total chlorine content was 557 ppm.

Example 7 Synthesis of 5,7-dimethyl-1,3-bis(glycidyloxy)adamantane

An operation was conducted in the same manner as in Example 5 exceptthat 16.8 g (0.10 mol) of 1,3-adamantanediol was replaced by 19.6 g(0.10 mol) of 5,7-dimethyl-1,3-adamantanediol, whereby was obtained 2.13g (yield: 6.9%) of a white compound and oily matter. This compound wassubjected to MASS spectrometry, ¹H-NMR spectrometry and elementalanalysis. As a result, the compound was confirmed to be intended5,7-dimethyl-1,3-bis(glycidyloxy)adamantane. The results of analyses areshown below.

MASS (EI): molecular weight 308 (M⁺)

¹H-NMR: δ 1.1-2.0 (m, 18H), 2.7-4.1 (m, 10H)

Elemental analysis: as C₁₈H₂₈O₄

Calculated: C 70.10, H 9.15

Measured: C 70.35, H 9.03

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 710 ppm, the inorganic chlorine content was 12 ppmand the total chlorine content was 722 ppm.

Example 8 Synthesis of 1,3,5-tris(glycidyloxy)adamantane

An operation was conducted in the same manner as in Example 1 exceptthat, in Example 5, 16.8 g (0.10 mol) of 1,3-adamantanediol was replacedby 18.4 g (0.10 mol) of 1,3,5-adamantanetriol, the amount of sodiumhydride was changed to 7.9 g (0.33 mol), and the amount ofepichlorohydrin was changed to 30.5 g (0.33 mol), to obtain 1.5 g(yield: 4.2%) of a white solid and oily matter. This compound wassubjected to MASS spectrometry, ¹H-NMR spectrometry and elementalanalysis. As a result, the compound was confirmed to be intended1,3,5-tris(glycidyloxy)adamantane. The results of analyses are shownbelow.

MASS (EI): molecular weight 352 (M⁺)

¹H-NMR: δ 1.1-2.0 (m, 13H), 2.7-4.1 (m, 15H)

Elemental analysis: as C₁₉H₂₈O₆

Calculated: C 64.75, H 8.01

Measured: C 65.11, H 8.23

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 550 ppm, the inorganic chlorine content was 23 ppmand the total chlorine content was 573 ppm.

Example 9 Synthesis of 2,3,5-tri(glycidyloxy)norbornane

An operation was conducted in the same manner as in Example 1 exceptthat, in Example 6, 12.8 g (0.10 mol) of 2,5-norbornanediol was replacedby 14.4 g (0.10 mol) of 2,3,5-norbornanetriol, the amount of sodiumhydride was changed to 7.9 g (0.33 mol), and the amount ofepichlorohydrin was changed to 30.5 g (0.33 mol), to obtain 1.6 g(yield: 5.0%) of a white solid and oily matter. This compound wassubjected to MASS spectrometry, ¹H-NMR spectrometry and elementalanalysis. As a result, the compound was confirmed to be intended2,3,5-tris(glycidyloxy)norbornane. The results of analyses are shownbelow.

MASS (EI): molecular weight 312 (M⁺)

¹H-NMR: δ 1.1-2.0 (m, 9H), 2.7-4.1 (m, 15H)

Elemental analysis: as C₁₆H₂₄O₆

Calculated: C 61.52, H 7.74

Measured: C 61.50, H 7.69

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 670 ppm, the inorganic chlorine content was 34 ppmand the total chlorine content was 704 ppm.

Example 10 Synthesis of 1,3-bis(glycidyloxymethyl)adamantane

300 ml of dehydrated tetrahydrofuran containing 19.6 g (0.1 mol) of1,3-bis(hydroxymethyl)adamantane and 5.3 g (0.22 mol) of sodium hydridewas stirred in a nitrogen atmosphere at the reflux temperature for 2hours. Thereto was dropwise added 20.4 g (0.22 mol) of epichlorohydrin,followed by stirring at the reflux temperature for 12 hours. To thereaction mixture was added 200 ml of chloroform, followed by washingwith water. The chloroform layer was dried with magnesium sulfate. Thedried chloroform layer was subjected to distillation under reducedpressure for solvent removal, whereby was obtained a white solid andoily matter.

This was purified by silica gel column chromatography to obtain 1.9 g(yield: 6.7%) of a white solid and oily matter.

This compound was subjected to MASS spectrometry, ¹H-NMR spectrometryand elemental analysis. As a result, the compound was confirmed to beintended 1,3-bis(glycidyloxymethyl)adamantane. The results of analysesare shown below.

MASS (EI): molecular weight 308 (M⁺)

¹H-NMR: δ 1.1-2.0 (m, 14H), 2.5-4.1 (m, 14H)

Elemental analysis: as C₁₈H₂₈O₄

Calculated: C 70.10, H 9.15

Measured: C 70.36, H 9.32

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 800 ppm, the inorganic chlorine content was 20 ppmand the total chlorine content was 820 ppm.

Example 11 Synthesis of oligomer of1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane

56.4 g (0.22 mol) of 3-ethyl-3-p-toluenesulfonyloxymethyloxetane wasadded to 300 ml of dehydrated tetrahydrofuran containing 16.8 g (0.1mol) of 1,3-adamantanediol and 5.3 g (0.22 mol) of sodium hydride, in anitrogen atmosphere, followed by stirring at the reflux temperature for2 hours. Thereto was added 36.5 g (0.22 mol) of potassium iodide,followed by stirring at the reflux temperature for 12 hours. To thereaction mixture was added 200 ml of chloroform. The chloroform layerwas washed with water and then dried with magnesium sulfate. The driedchloroform layer was subjected to distillation under reduced pressurefor solvent removal, to obtain a white solid and oily matter.

This was purified by silica gel column chromatography to obtain 5.39 gof a white solid and oily matter. This compound was subjected to gelpermeation chromatography (hereinafter, referred to as GPC), whichindicated a peak at around 660 to 680 (molecular weight) (Mw/Mn=1.11).From this result, the compound was confirmed to be a dimer of1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane.

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 220 ppm, the inorganic chlorine content was 20 ppmand the total chlorine content was 240 ppm.

Example 12 Synthesis of oligomer of2,5-bis[(3-ethyloxetan-3-yl)methoxy]norbornane

56.4 g (0.22 mol) of 3-ethyl-3-p-toluenesulfonyloxymethyloxetane wasadded to 300 ml of dehydrated tetrahydrofuran containing 12.8 g (0.1mol) of 2,5-norbornanediol and 5.3 g (0.22 mol) of sodium hydride, in anitrogen atmosphere, followed by stirring at the reflux temperature for2 hours. Thereto was added 36.5 g (0.22 mol) of potassium iodide,followed by stirring at the reflux temperature for 12 hours. To thereaction mixture was added 200 ml of chloroform. The chloroform layerwas washed with water and then dried with magnesium sulfate. The driedchloroform layer was subjected to distillation under reduced pressurefor solvent removal, to obtain a white solid and oily matter.

This was purified by silica gel column chromatography to obtain 6.01 gof a white solid and oily matter. This compound was subjected to GPC,which indicated a peak at around 580 to 600 (molecular weight)(Mw/Mn=1.12). From this result, the compound was confirmed to be a dimerof 2,5-bis[(3-ethyloxetan-3-yl)methoxy]norbornane.

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 300 ppm, the inorganic chlorine content was 25 ppmand the total chlorine content was 325 ppm.

Example 13 Synthesis of 1,3-bis(glycidyloxy)adamantane

400 ml of dimethylformamide containing 70 g (0.42 mol) of1,3-adamantanediol and 30 g (1.25 mols) of sodium hydride was stirred ina nitrogen atmosphere at 70° C. for 2 hours. The resulting mixture wascooled to room temperature. Thereto was dropwise added 151 g (1.25 mols)of allyl bromide in 4 hours, followed by stirring at room temperaturefor 12 hours. 200 ml of water was added and extraction was made using500 ml of methylene chloride. The organic layer was washed with waterand then subjected to distillation for removal of methylene chloride.Distillation was conducted under reduced pressure for solvent removal,and it was continued to obtain 69 g (0.28 mol, purity: 67%) of1,3-bis(allyloxy)adamantane.

This was dissolved in 400 ml of methylene chloride. Thereto was added111 g (0.64 mol) of m-perchlorobenzoic acid, followed by stirring atroom temperature overnight. An aqueous sodium sulfite solution was addedfor decomposition of excessive peracid. The separated m-chlorobenzoicacid was removed by filtration. The organic layer was washed with anaqueous sodium hydroxide solution and water in this order. Methylenechloride was removed by distillation, after which distillation underreduced pressure was conducted to obtain 35 g (0.125 mol, yield: 45%) of1,3-bis(glycidyloxy)adamantane.

This compound was subjected to MASS spectrometry, ¹H-NMR spectrometryand elemental analysis. As a result, the compound was confirmed to beintended 1,3-bis(glycidyloxy)adamantane. The results of analyses areshown below.

MASS (EI): molecular weight 280 (M⁺)

¹H-NMR: 1.47 (s. 2H), 1.65 (s. 8H), 1.73 (s. 2H), 2.30 (s. 2H), 2.57 (dd2H), 2.76 (dd. 2H), 3.06 (m. 2H), 3.41 (dd. 2H), 3.58 (dd. 2H)

The compound was measured for inorganic chlorine content by the methodfor determination of saponifiable chlorine, described in ISO 4583 andthe method described in ISO 4573. The result was that the organicchlorine content was 130 ppm, the inorganic chlorine content was 13 ppmand the total chlorine content was 143 ppm.

Example 14 Synthesis of 5,7-difluoro-1,3-bis(glycidyloxy)adamantane

Using 5 g (24 mmol) of 5,7-difluoro-1,3-adamantanediol, 1.8 g (75 mmol)of sodium hydride, 25 ml of dimethylformamide and 9 g (75 mmol) of allylbromide, a reaction was conducted in a nitrogen atmosphere in the samemanner as in Example 13, to obtain 5.1 g (18 mmol) of5,7-difluoro-1,3-bis(allyloxy)adamantane.

This was dissolved in 50 ml of methylene chloride. Thereto was added 7 g(41 mmol) of m-perchlorobenzoic acid, and a reaction was conducted inthe same manner as in Example 13.

The reaction product was purified by silica gel column chromatography toobtain 4.7 g (15 mmol, yield: 63%) of5,7-difluoro-1,3-bis(glycidyloxy)adamantane.

MASS (EI): molecular weight 316 (M⁺)

¹H-NMR: 1.0-2.5 (m. 12H), 2.5-4.1 (m. 10H)

Example 15 Synthesis of 5-butyl-1,3-bis(glycidyloxy)adamantane

Using 5 g (22 mmol) of 5-butyl-1,3-adamantanediol, 1.5 g (62 mmol) ofsodium hydride, 25 ml of dimethylformamide and 7 g (58 mmol) of allylbromide, a reaction was conducted in a nitrogen atmosphere in the samemanner as in Example 13, to obtain 5.3 g (17 mmol) of5-butyl-1,3-bis(allyloxy)adamantane.

This was dissolved in 50 ml of methylene chloride. Thereto was added 7 g(41 mmol) of m-chloroperbenzoic acid, and a reaction was conducted inthe same manner as in Example 13.

The reaction product was purified by silica gel column chromatography toobtain 4.7 g (14 mmol, yield: 64%) of5-butyl-1,3-bis(glycidyloxy)adamantane.

MASS (EI): molecular weight 336 (M⁺)

¹H-NMR: 0.7-2.5 (m. 22H), 2.5-4.1 (m. 10H)

Next, the curable polycyclic compounds obtained in the present Examplesand Comparative Examples were cured, and the cured materials weremeasured for the following properties according to the followingevaluation methods.

(1) Light Resistance

A light containing a ultraviolet light was applied to a test piece(initial stage: almost colorless and transparent) for 500 hours, using axenon weatherometer (X 25, a product of Sugai Shikenki). After the lightapplication, the discoloration of the test piece was examined visuallyand rated in two levels.

(A) Slight yellowing

(B) Severe yellowing

(2) Heat Resistance

A test piece (initial stage: almost colorless and transparent) wasallowed to stand in an oven of 150° C. for 100 hours. Thereafter, thediscoloration of the test piece was examined visually and rated in twolevels.

(A) Slight yellowing

(B) Severe yellowing

Example 16

36 g (0.1 mol) of the 1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane and16 g (95 mmol) of 3-methylhexahydrophthalic anhydride as a curing agentwere mixed and stirred until they became uniform. Thereto was added 0.16g of tetrabutylphosphonium diethylphosphorodithioate as a curingcatalyst, followed by mixing. The mixture was poured into between twoglass plates and cured at 120° C. for 3 hours. The gap between the twoglass plates was 5 mm. An almost transparent flat plate (test piece 1)of 5 mm in thickness was obtained.

This test piece 1 was evaluated for light resistance and heat resistanceaccording to the above test methods. The results are shown in Table 1.

Examples 17 to 31

Test pieces 2 to 15 were produced in the same manner as in Example 16,using the curable polycyclic compounds obtained in Examples 2 to 15.These test pieces 2 to 15 were evaluated for light resistance and heatresistance according to the above test methods. The results are shown inTable 1.

Example 31

A test piece 16 was produced in the same manner as in Example 16 exceptthat there were used, as a curable polycyclic compound, the2,5-bis(glycidyloxy)norbornane obtained in Example 6, in the same amount(mol) as in Example 16 and, as a curing agent, hexahydrophthalicanhydride. The evaluation results therefor are shown in Table 1.

Example 32

A test piece 17 was produced in the same manner as in Example 16 exceptthat there was used, as a curing catalyst, 0.15 g of triphenylsulfoniumhexafluorophosphate. The evaluation results therefor are shown in Table1.

Example 33

A test piece 18 was produced in the same manner as in Example 16 exceptthat there were used, as a curable polycyclic compound, the dimer of1,3-bis[(3-ethyloxetan-3-yl)methoxy]adamantane obtained in Example 11,in the same amount (mol) as in Example 16 and, as a curing agent, 16 gof 3-methylhexahydrophthalic anhydride. The evaluation results thereforare shown in Table 1.

Example 34

A test piece 19 was produced in the same manner as in Example 16 exceptthat there were used, as a curable polycyclic compound, the dimer of2,5-bis[(3-ethyloxetan-3-yl)methoxy]norbornane obtained in Example 12,in the same amount (mol) as in Example 16 and, as a curing agent, 16 gof 3-methylhexahydrophthalic anhydride. The evaluation results thereforare shown in Table 1.

Comparative Example 1

An almost transparent flat plate (test piece 20) of 5 mm in thicknesswas obtained in the same manner as in Example 16 except that there wasused, as a curable compound, 34 g of bisphenol A glycidyl ether. Theresults therefor are shown in Table 1.

Comparative Example 2

An almost transparent flat plate (test piece 21) of 5 mm in thicknesswas obtained in the same manner as in Example 16 except that there wasused, as a curable compound, 35.2 g of hydrogenated bisphenol A glycidylether. The results therefor are shown in Table 1. TABLE 1 No. of LightHeat test piece resistance resistance Example 16 1 A A Example 17 2 A AExample 18 3 A A Example 19 4 A A Example 20 5 A A Example 21 6 A AExample 22 7 A A Example 23 8 A A Example 24 9 A A Example 25 10 A AExample 26 11 A A Example 27 12 A A Example 28 13 A A Example 29 14 A AExample 30 15 A A Example 31 16 A A Example 32 17 A A Example 33 18 A AExample 34 19 A A Comparative 23 B A Example 1 Comparative 24 A BExample 2

Example 35 Synthesis of 1,3-bis(glycidyloxy)adamantane

In a 200-ml three-necked flask were placed 5.04 g (0.03 mol) of1,3-adamantanediol and 25 ml of N,N-dimethylformamide. 3.6 g (0.09 mol)of sodium hydride (60% by mass)/liquid paraffin was washed with hexane 5times and was added to the flask contents with stirring under watercooling. The mixture was heated to 70° C. and stirred for 3 hours. Then,the flask contents were cooled to 5° C. Thereto was dropwise added 10.9g (0.09 mol) of allyl bromide slowly. After the dropwise addition, themixture was stirred at 5° C. for 2 hours. Thereafter, 10 ml of water wasadded to complete a reaction.

To the reaction mixture was added 100 ml of tetrahydrofuran to conductextraction. The organic layer was washed with water 3 times. The organiclayer was subjected to distillation under reduced pressure using arotary evaporator to remove tetrahydrofuran and N,N-dimethylformamide asmuch as possible. The resulting liquid was subjected to distillation at0.1 mmHg at 105° C., to obtain a colorless transparent liquid.

The liquid was subjected to MASS spectrometry, ¹H-NMR spectrometry andelementary analysis. As a result, the compound was confirmed to be1,3-bis(2-propenyloxy)adamantane. The results of analyses are shownbelow.

MASS (EI): molecular weight 248 (M⁺)

¹H-NMR (TMS standard): δ 1.1-2.0 (m, 14H), 4.0-4.3 (m, 4H), 5.2-5.9 (m,6H)

Elemental analysis: as C₁₆H₂₄O₂

Calculated: C 77.38, H 9.74

Measured: C 77.76, H 9.63

The obtained 1,3-bis(2-propenyloxy)adamantane {5.96 g, yield: 80.1%,purity by gas chromatography: 96.0%, purity by gel permeationchromatography (hereinafter referred to as GPC): 99.5%} was dissolved in30 ml of dichloromethane. Thereto was added 14.3 g (0.058 mol) of 70%m-chloroperbenzoic acid, followed by stirring at room temperature for 16hours. Then, the reaction mixture was washed with 30 ml of a 25% aqueoussodium sulfite solution and further with water twice. The reactionmixture was subjected to distillation to remove dichloromethane, wherebywas obtained crude 1,3-bis(glycidyloxy)adamantane {6.70 g, yield: 79.8%(from adamantanediol), purity by gas chromatography: 96.1%, GPC purity:99.7%, colorless liquid}. The liquid was subjected to distillation at0.1 mmHg at 140° C. to obtain, as a colorless transparent liquid,1,3-bis(glycidyloxy)adamantane {5.36 g, yield: 63.8% (fromadamantanediol), purity by gas chromatography: 98.3%, GPC purity:99.8%}.

Example 36

An operation was conducted in the same manner as in Example 35 exceptthat the allyl bromide used in Example 35 was replaced by 6.89 g (0.09mol) of allyl chloride and, after the dropwise addition of allylchloride, stirring was conducted at 5° C. for 5 hours. As a result,after purification by distillation, there was obtained, as a colorlesstransparent liquid, 1,3-bis(2-propenyloxy)adamantane {5.36 g, yield:72.0%, purity by gas chromatography: 95.9%, GPC purity: 99.4%}. Theamount of crude 1,3-bis(glycidyloxy)adamantane before purification bydistillation was 5.99 g {yield: 71.3% (based on adamantanediol), purityby gas chromatography: 96.1%, GPC purity: 99.4%, colorless liquid}. Theamount of colorless transparent liquid 1,3-bis(glycidyloxy)adamantaneafter purification by distillation was 4.67 g {yield: 55.6% (based onadamantanediol), purity by gas chromatography: 98.5%, GPC purity:99.8%}.

Example 37

An operation was conducted in the same manner as in Example 35 exceptthat the 70% m-chloroperbenzoic acid used in Example 35 was replaced by76.1 g (0.09 mol) of 9% peracetic acid and stirring was conducted atroom temperature for 20 hours.

As a result, after purification by distillation, there was obtained, asa colorless transparent liquid, 1,3-bis(2-propenyloxy)adamantane {6.03g, yield: 81.0%, purity by gas chromatography: 95.7%, GPC purity:99.5%}. The amount of crude 1,3-bis(glycidyloxy)adamantane beforepurification by distillation was 6.04 g {yield: 71.9% (fromadamantanediol), purity by gas chromatography: 96.5%, GPC purity: 99.4%,colorless liquid}. The amount of colorless transparent liquid1,3-bis(glycidyloxy)adamantane after purification by distillation was4.84 g {yield: 57.5% (from adamantanediol), purity by gaschromatography: 98.6%, GPC purity: 99.7%).

Example 38 Synthesis of 2,5-bis(glycidyloxy)norbornane

An operation was conducted in the same manner as in Example 35 exceptthat the 1,3-adamantanediol used in Example 35 was replaced by 3.84 g(0.03 mol) of 2,5-norbrnanediol. The compound after purification wassubjected to MASS spectrometry, ¹H-NMR spectrometry and elementalanalysis. As a result, the compound was confirmed to be2,5-bis(2-propenyloxy)norbornane. The results of analyses are shownbelow.

MASS (EI): molecular weight 208 (M⁺)

¹H-NMR (TMS standard): δ 1.1-2.0 (m, 10H), 4.0-4.3 (m, 4H), 5.2-5.9 (m,6H)

Elemental analysis: as C₁₃H₂₀O₂

Calculated: C 74.96, H 9.68

Measured: C 74.81, H 9.62

The obtained 2,5-bis(2-propenyloxy)norbornane (5.06 g, yield: 81.1%,purity by gas chromatography: 96.1%, GPC purity: 99.4%) was subjected tothe same operation as in Example 35, for oxidation. As a result, theamount of crude 2,5-bis(glycidyloxy)norbornane before purification was5.74 g {yield: 79.7% (based on norbornanediol), purity by gaschromatography: 96.2%, GPC purity: 99.6%}. The amount of2,5-bis(glycidyloxy)norbornane after purification was 4.69 g {yield:65.1% (based on norbornanediol), purity by gas chromatography: 98.2%,GPC purity: 99.7%}.

Example 39 Synthesis of 1,3,5-tris(glycidyloxy)adamantane

An operation was conducted in the same manner as in Example 35 exceptthat the 1,3-adamantanediol used in Example 35 was replaced by 5.52 g(0.03 mol) of 1,3,5-adamantanetriol. The compound after purification wassubjected to MASS spectrometry, ¹H-NMR spectrometry and elementalanalysis. As a result, the compound was confirmed to be1,3,5-tris(2-propenyloxy)adamantane.

The results of analyses are shown below.

MASS (EI): molecular weight 304 (M⁺)

¹H-NMR: δ 1.1-2.0 (m, 13H), 4.0-4.3 (m, 6H), 5.2-5.9 (m, 9H)

Elemental analysis: as C₁₉H₂₈O₃

Calculated: C 74.96, H 9.27

Measured: C 74.56, H 9.54

The obtained 1,3,5-tris(2-propenyloxy)adamantane (6.39 g, yield: 70.1%,purity by gas chromatography: 96.2%, GPC purity: 99.5%) was subjected tothe same operation as in Example 35, for oxidation. As a result, theamount of crude 1,3,5-tris(glycidyloxy)adamantane before purificationwas 7.09 g {yield: 67.2% (from adamantanetriol), purity by gaschromatography: 96.5%, GPC purity: 99.5%}. The amount of1,3,5-tris(glycidyloxy)adamantane after purification was 5.29 g {yield:50.1% (from adamantanetriol), purity by gas chromatography: 98.5%, GPCpurity: 99.8%}.

Example 40 Synthesis of 2,3,5-tris(glycidyloxy)norbornane

An operation was conducted in the same manner as in Example 35 exceptthat the 1,3-adamantanediol used in Example 35 was replaced by 4.32 g(0.03 mol) of 2,3,5-norbrnanetriol. The compound after purification wassubjected to MASS spectrometry, ¹H-NMR spectrometry and elementalanalysis. As a result, the compound was confirmed to be2,3,5-tris(glycidyloxy)norbornane. The results of analyses are shownbelow.

MASS (EI): molecular weight 264 (M⁺)

¹H-NMR: δ 1.1-2.0 (m, 9H), 4.0-4.3 (m, 6H), 5.2-5.9 (m, 9H)

Elemental analysis: as C₁₆H₂₄O₃

Calculated: C 72.69, H 9.15

Measured: C 72.50, H 9.39

The obtained 2,3,5-tris(2-propenyloxy)norbornane (5.33 g, yield: 67.3%,purity by gas chromatography: 96.4%, GPC purity: 99.5%) was subjected tothe same operation as in Example 35, for oxidation. As a result, theamount of crude 2,3,5-tris(glycidyloxy)norbornane before purificationwas 5.63 g (yield: 60.2% (based on norbornanetriol), purity by gaschromatography: 96.5%, GPC purity: 99.6%}. The amount of2,3,5-tris(glycidyloxy)norbornane after purification was 4.35 g {yield:46.5% (based on norbornanetriol), purity by gas chromatography: 98.5%,GPC purity: 99.7%}.

Comparative Example 3

In a 200-ml three-necked flask were placed 5.04 g (0.03 mol) of1,3-adamantanediol, 0.2 ml of anhydrous tin tetrachloride and 30 ml ofcarbon tetrachloride. The mixture was stirred at 5° C. Thereto wasdropwise added 6.64 g of epichlorohydrin. After the dropwise addition,stirring was conducted under refluxing for 5 hours. The reaction mixturewas allowed to cool and then 40 ml of a 5% aqueous sodium hydroxidesolution was added to complete a reaction. The reaction mixture waswashed with water 3 times, after which the solvent was removed bydistillation to obtain 16.2 g of a yellow viscous liquid. This yellowviscous liquid was dissolved in 20 ml of 2-propanol. Thereto wasdropwise added an aqueous sodium hydroxide solution (3 g of sodiumhydroxide dissolved in 3 g of water) at room temperature, followed bystirring for 3 hours. Then, 50 ml of water and 50 ml of ethyl acetatewere added to conduct extraction. The organic layer was washed withwater 2 times, and the solvent was removed by distillation to obtain10.8 g of a yellow liquid. This crude 1,3-bis(glycidyloxy)adamantane hada gas chromatography purity of 54.4% and a GPC purity of 30.2% andcontained a large amount of a high-molecular compound.

The crude product was subjected to distillation under. reduced pressure(0.1 mmHg, oil bath temperature: 175° C.). However,1,3-bis(glycidyloxy)adamantane was unobtainable and the flask contentscured and became gel-like.

1. (canceled)
 2. (canceled)
 3. (canceled)
 4. (canceled)
 5. (canceled) 6.(canceled)
 7. (canceled)
 8. (canceled)
 9. (canceled)
 10. (canceled) 11.(canceled)
 12. A curable polycyclic compound represented by thefollowing formula (1):

{wherein A is a di- to hexa-valent group derived from a polycyclichydrocarbon compound; R¹ is an alkyl group of 1 to 4 carbon atoms, aperfluoroalkyl group of 1 to 4 carbon atoms, or a fluorine atom; n is aninteger of 0 to 2; m is an integer of 2 to 4; and Y is a grouprepresented by the following formula (2):

(wherein R² and R³ are each independently a hydrogen atom, a fluorineatom or an alkyl group of 1 to 4 carbon atoms; R⁴ is a methyl group oran ethyl group; and p is an integer of 0 to 4), or a group representedby the following formula (3):

(wherein R⁵ and R⁶ are each independently a hydrogen atom, a fluorineatom or an alkyl group of 1 to 4 carbon atoms; and q is an integer of 0to 4)}; wherein the following formula (4):

{wherein R¹ is an alkyl group of 1 to 4 carbon atoms, a perfluoroalkylgroup of 1 to 4 carbon atoms, or a fluorine atom; a is an integer of 0to 2; b is an integer of 0 to 2; and Y is a group represented by thefollowing formula (3.1):


13. A curable polycyclic compound according to claim 12, wherein, in theformula (4), a is 0 (zero).
 14. A curable polycyclic compound accordingto claim 12, wherein the content of the halogen molecule or halogen ioncontained as an impurity is 100 to 2,000 ppm.
 15. A curable polycycliccompound represented by the general formula (7.1):

{wherein R¹, Y, a and b have the same definitions as in the formula (4);and s′ is an integer of 1 to 3}.
 16. A curable composition characterizedby comprising a curable polycyclic compound set forth in any of claim 12and a curing agent.
 17. An encapsulant for light-emitting diode,comprising a curable composition set forth in claim
 16. 18. Alight-emitting diode encapsulated by an encapsulant set forth in claim17.
 19. A process for producing a polycyclic epoxy compound representedby the following formula (8.1):

{wherein R¹ is an alkyl group of 1 to 4 carbon atoms, a perfluoroalkylgroup of 1 to 4 carbon atoms, or a fluorine atom; a is an integer of 0to 2; b is an integer of 0 to 2; and Y is a group represented by thefollowing formula (3.1)}:

, which process is characterized by comprising the following steps (a)to (c): a step (a) of reacting a polycyclic hydroxy compound representedby the following formula (9.1):

{wherein R¹, a and b have the same definitions as in the formula (8.1)},with an alkali metal or an alkaline metal hydride to obtain analcoholate, a step (b) of reacting the alcoholate obtained in the step(a), with an allyl group-containing compound represented by thefollowing formula (10):X—CH₂—CH═CH₂  (10) (wherein X is a halogen atom or a sulfonyloxy group)to obtain a polycyclic allyl compound represented by the followingformula (11.1):

[wherein R¹, a and b have the same definitions as in the formula (8.1);and W is a group represented by the following formula (12.1)]:O—CH₂—CH═CH₂  (12.1) , and a step (c) of oxidizing the polycyclic allylcompound obtained in the step (b).
 20. A polycyclic allyl compoundrepresented by the following formula (11.1):

{wherein R¹ is an alkyl group of 1 to 4 carbon atoms, a perfluoroalkylgroup of 1 to 4 carbon atoms, or a fluorine atom; a is an integer of 0to 2; b is an integer of 0 to 2; and W is a group represented by thefollowing formula (12.1):—O—CH₂—CH═CH₂  (12.1)